EP2290140B1 - Fil torsadé en polytétrafluoréthylène réel et son procédé de production - Google Patents

Fil torsadé en polytétrafluoréthylène réel et son procédé de production Download PDF

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Publication number
EP2290140B1
EP2290140B1 EP10006252A EP10006252A EP2290140B1 EP 2290140 B1 EP2290140 B1 EP 2290140B1 EP 10006252 A EP10006252 A EP 10006252A EP 10006252 A EP10006252 A EP 10006252A EP 2290140 B1 EP2290140 B1 EP 2290140B1
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EP
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Prior art keywords
ptfe
yarn
range
film
real twist
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German (de)
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EP2290140A1 (fr
Inventor
James Huang
Chin-Chun Chou
Chin-Cha Chou
Wen-I Kuo
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Yeu Ming Tai Chemical Industrial Co Ltd
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Yeu Ming Tai Chemical Industrial Co Ltd
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/06—Threads formed from strip material other than paper
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
    • D10B2321/042—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]

Definitions

  • the present invention relates to a polytetrafluoroethylene (PTFE) real twist yarn and a method of producing the same.
  • PTFE polytetrafluoroethylene
  • U.S. Pat. No. 2,772,444 proposes a method of producing PTFE fibers by emulsion spinning of a mixed solution of an aqueous dispersion solution of PTFE fine particles and viscose, followed by sintering of the PTFE at high temperatures to remove the viscose by thermal decomposition.
  • the cost of producing PTFE fibers by using this method is high, whereas the strength of the fibers obtained is low, and therefore the strength of products obtained by processing the fibers as a raw material is also low.
  • U.S. Pat. Nos. 3,953,566 and 4,187,390 propose a method of obtaining PTFE fibers by slitting a PTFE film or sheet into a minute width, followed by stretching of the obtained tape.
  • this method it is difficult to maintain the width of the tape obtained by slitting the film or sheet uniformly along the length direction. Also an end portion of the tape tends to be fibrillated. For these reasons, some fibers get ruptured during a step of stretching the tape to a high degree.
  • JP 2004-244787 A and JP 2006-124899 A propose a method of obtaining high-strength PTFE fibers by slitting a PTFE stretched film or sheet into a minute width, followed by stretching of the obtained tape.
  • an end portion of the tape tends to be fibrillated, and as a result, some fibers get ruptured during a step of stretching the tape to a high degree.
  • JP H07-500386 A ( EP-A-0 608236 ) discloses a yarn obtained by helically rolling a PTFE film or sheet and causing the film or sheet to adhere to itself.
  • the yarn has a spiral seam on its surface along the length direction.
  • U.S. Pat. No. 5,765,576 discloses a PTFE filament whose surface area is increased by towing in order to make the filament friction resistant.
  • the problem of this PTFE filament is that it has a flat cross-section.
  • a PTFE yarn according to the preamble is disclosed in EP-A-0768394 .
  • the present invention provides a PTFE real twist yarn having a substantially circular (round) cross-section and a method of producing the same.
  • the PTFE real twist yarn of the present invention is a polytetrafluoroethylene (PTFE) real twist yarn obtained by twisting a PTFE multi-filament slit yarn.
  • the method of producing a PTFE real twist yarn of the present invention produces a PTFE real twist yarn by twisting a PTFE multi-filament slit yarn using a yarn-twisting machine.
  • the PTFE real twist yarn has a circular cross-section with a circularity in a range of 10/8 to 10/10, where the circularity is expressed by a ratio between a major axis width and a minor axis width of the cross-section, an average fineness of filaments is in a range of 1.5 to 200 dtex, a fineness D is in a range of 50 to 6000 dtex, and a twist coefficient K expressed by Formula (1) is in a range of 10000 to 35000.
  • the number of Filaments is in a range of 10 to 200, and the yarn has a tensile strength in a range of 1.7 to 4.5 CN/dtex and an elongation in a range of 3.5 to 40%.
  • a PTFE real twist yarn having a circular cross-section by twisting a PTFE multi-filament slit yarn, a PTFE real twist yarn having a circular cross-section, a fineness D in the range of 50 to 6000 dtex and a twist coefficient K in the range of 10000 to 35000 is produced.
  • a real twist yarn suitable for, e.g., a sewing yarn or dental floss can be obtained.
  • the PTFE real twist yarn can be produced effectively and stably through a simple process at a relatively low cost.
  • the PTFE real twist yarn of the present invention has a circular cross-section.
  • the term “circular” refers to a substantially circular shape. Thus, not only a perfectly circular shape but also a roughly circular shape falls within the meaning of the term "circular'.
  • the circular cross-section has a circularity in the range of 10/8 to 10/10, which is expressed by the ratio between the major axis width and the minor axis width. Further, in terms of suppressing the occurrence of fuzz, the circularity is preferably in the range of 10/9 to 10/10 and more preferably 10/10.
  • the "ratio between the major axis width and the minor axis width of cross-section" is measured as follows.
  • the PTFE real twist yarn of the present invention is a composition of filaments.
  • the PTFE real twist yarn 41 contains a plurality of filaments 42.
  • the term "filament” refers to a fiber that cannot be split anymore.
  • the average fineness of the filaments is in the range of 1.5 to 200 dtex.
  • the real twist yarn is likely to have a circular cross-section and the side of the yarn is likely to become smooth.
  • a PTFE multi-filament slit yarn is less likely to be obtained.
  • a real twist yarn having a circular cross-section is less likely to be obtained and filaments with a large fineness tend to stick out from the side of the yarn.
  • the average fineness of the filaments is preferably in the range of 7.5 to 150 dtex and more preferably in the range of 20 to 40 dtex because a circular cross-section is more likely to be obtained and the side of the yarn is likely to become smooth.
  • the number of the filaments contained in the PTFE real twist yarn is in the range of 10 to 200 and preferably in the range of 30 to 100.
  • the number of the filaments is 10 or more, the fineness of the filaments does not become too large, so that the cross-section is likely to become circular and also the side of the yarn is likely to become smooth.
  • the number of the filaments is 200 or less, the fineness of the filaments does not become too small, so that the cross-section is likely to become circular and also the side of the yarn is likely to become smooth.
  • the fineness D of the PTFE real twist yarn is in the range of 50 to 6000 dtex and preferably in the range of 400 to 3200 dtex.
  • the fineness D refers to a total fineness which is expressed in dtex.
  • the twist coefficient K of the PTFE real twist yarn expressed by Formula (1) is in the range of 10000 to 35000 and more preferably in the range of 11000 to 24000.
  • the twist coefficient K is less than 10000, the yarn tends to become a so-called loose twist yarn, so that a firm and tight twist structure and a circular cross-section are less likely to be obtained.
  • a yarn having a twist coefficient K of more than 35000 is a strong twist yarn, which requires a high production cost and a circular cross-section is less likely to be obtained. Furthermore, there is less market demand for the development of strong twist yarns having a twist coefficient K of more than 35000.
  • the PTFE multi-filament slit yarn is a composition of filaments and has a fibril structure.
  • the filaments get partially defibrillated, thereby forming a network and/or branch structure.
  • FIGS. 1 and 2 show examples of the network structure. The numerical values shown on the scale on the left side of FIGS. 1 and 2 are in the unit of cm.
  • the network cells vary in size and shape depending upon the stretch ratio of a PTFE film used in the production of the PTFE multi-filament slit yarn or the embossed shape formed during the embossing, overall, the network structure has an uniform and stable shape.
  • the length of filaments forming the network structure is in the range of 3 to 50 mm and preferably in the range of 5 to 30 mm.
  • the size (major axis ⁇ minor axis) of a single network cell is in the range of 10 mm ⁇ 7 mm to 50 mm ⁇ 20 mm.
  • the PTFE real twist yarn of the present invention is obtained by twisting the PTFE multi-filament slit yarn. Therefore, similarly to the PTFE multi-filament slit yarn, when the PTFE real twist yarn is spread in the width direction, the filaments get partially defibrillated, thereby forming a network and/or branch structure.
  • the PTFE a multi-filament slit yarn may be a long slit yarn (hereinafter referred to as a long PTFE multi-filament slit yarn) or short slit yarn (hereinafter referred to as a short PTFE multi-filament slit yarn).
  • the long PTFE multi-filament slit yarn refers to a slit yarn having substantially the same length as a PTFE film to be used in the production of the PTFE multi-filament slit yarn.
  • the length of the PTFE film is not particularly limited, it is practical that the length is in the range of about 1000 to 10000 m, for example.
  • the short PTFE multi-filament slit yarn is obtained by cutting the long PTFE multi-filament slit yarn having a network structure to a given length perpendicularly to the length direction.
  • the length of the short PTFE multi-filament slit yarn is not particularly limited but is preferably in the range of 10 to 60 mm and more preferably in the range of 20 to 40 mm.
  • the short PTFE multi-filament slit yarn 4 has a branch structure as the network structure gets partially ruptured.
  • the term "filament” refers to a fiber that cannot be split anymore.
  • the term "filament” refers to a fiber that cannot be split anymore.
  • single fibers 2 forming the network structure are all filaments.
  • branched fibers 5a to 5f and a main-chain fiber 6 are all filaments.
  • the PTFE multi-filament slit yarn is preferably a PTFE multi-filament slit yarn having a roughly normal filament fineness distribution and high fineness uniformity
  • the "roughly normal fineness distribution” refers to such a distribution that, among a number of measurement samples (filaments), the number of samples in the region of the average fineness is the highest and the number of samples gradually decreases as moving away from the average fineness.
  • the PTFE multi-filament slit yarn preferably has a flat shape, a thickness in the range of 1.5 to 150 ⁇ m and a ratio between the thickness and width in the range of 1/3 to 1/300. From such a PTFE multi-filament slit yarn, a real twist yarn having a circular cross-section is likely to be obtained Further, it is more preferable that the PTFE multi-filament slit yarn has a thickness in the range of 15 to 150 ⁇ m and a ratio between the thickness and width in the range of 1/3 to 1/300 because a circular cross-section is more likely to be obtained.
  • a method by which the PTFE multi-filament slit yarn can be obtained is, but is not particularly limited to, as follows.
  • the embossed PTFE multi-filament slit yarn can be produced by using, but not particularly limited to, processes including a variety of steps as follows.
  • the unembossed PTFE multi-filament slit yarn can be produced in a manner similar to the embossed PTFE multi-filament slit yarn except that embossing is not performed
  • the original PTFE film can be produced by using a conventionally known method.
  • the original PTFE film is obtained by extruding a rod, bar or sheet shaped continuous extrudate through a paste extrusion process with the use of a PTFE fine powder and petroleum oil as an extrusion aid, followed by calendering the extrudate into a film shape with the use of one set of calendering rolls and performing heating or solvent extraction to remove the extrusion aid from the calendered film.
  • the PTFE fine powder can be obtained by, but is not particularly limited to, emulsion polymerization.
  • the mass mixing ratio of the PTFE fine powder to the extrusion aid is in the range of 80:20 to 77:23, and the reduction ratio (RR) in the paste extrusion is 300:1 or less. Further, heating is adopted in many cases to remove the extrusion aid and the temperature is preferably 300°C or less and particularly in the range of 250 to 280°C.
  • the PTFE multi-filament slit yarn is preferably stretched by 4 times or more in the length direction in the film and/or slit yarn state. This is to increase the strength.
  • the original PTFE film is an unstretched film or stretched film.
  • a stretched film is preferable because it has a higher strength.
  • the original PTFE film may be stretched uniaxially or biaxially.
  • the stretching ratio in the length direction of the film (LD) is 4 times or more and preferably 6 times or more.
  • the strength of a PTFE multi-filament slit yarn to be obtained increases as the stretching ratio is set higher.
  • the stretching ratio in LD is 4 times or more and preferably 6 times or more.
  • the stretching ratio in the width direction of the film (TD) perpendicular to LD is in the range of 1.5 to 15 times and preferably in the range of 2 to 3 times.
  • Biaxial stretching may be simultaneous stretching where the film is stretched simultaneously in LD and TD or two-stage stretching where the film is first stretched in LD and then is stretched in TD.
  • Relatively low density PTFE fibers can be obtained from defibrillation of a biaxially-stretched film, which allows a reduction in the price of the fibers and manufactured goods per mass.
  • the heat treatment of the PTFE film is performed at a temperature in the range of 327 to 450°C.
  • the heat treatment may be performed at a temperature in the range of 327 to 350°C, at a temperature in the range of 350 to 450°C for an extremely short period of time to semi-sinter the film or at a temperature in the range of 350 to 450°C to sinter the film.
  • the stretched PTFE film to be defibrillated may be any of unsintered, semi-sintered and sintered films, a semi-sintered or sintered film is preferable in terms of ease of handling as they are less likely to agglomerate.
  • the stretched PTFE film to be defibrillated has a thickness in the range of 1.5 to 150 ⁇ m and preferably in the range of 15 to 150 ⁇ m.
  • the PTFE film is preferably embossed and more preferably embossed linearly along the length direction and/or embossed in a zigzag or concave-convex shape in the width direction.
  • a film is made into a PTFE multi-filament slit yarn, an even and aligned network structure is likely to be obtained.
  • a real twist yarn is obtained by twisting such a slit yarn, the cross-section of the twist yarn is likely to become circular
  • An embossed pattern may be linear in the length direction of a stretched PTFE film and continuous in both the length and width directions.
  • the pitch between crests of the zigzag or concave-convex shape in the linear embossing is preferably in the range of 0.1 to 1.5 mm and more preferably in the range of 0.2 to 1.0 mm and it is particularly preferable when the pitch is in the range of 0.3 to 0.7 mm.
  • the difference in height (difference between top and bottom) of the zigzag or concave-convex shape in the linear embossing is preferably in the range of 0.2 to 1 mm and more preferably in the range of 0.3 to 0.8 mm.
  • Such a pattern can be formed by using an embossing roll.
  • linear embossing is not linear in the strict sense and only needs to be linear to such an extent that embossing workability is improved and the meaning thereof should be construed broadly
  • FIGS. 3A to 3B Examples of preferred embossed patterns in the present invention are as shown in FIGS. 3A to 3B.
  • FIG. 3A shows an example where embossed marks are formed on one side of a stretched PTFE film. These marks can be formed by increasing the hardness of an elastic roll 32 (rubber roll) described in FIG. 4 and reducing the linear load.
  • FIG. 3B shows an example where embossed marks are formed on the both sides of a stretched PTFE film. These marks can be formed by reducing the hardness of the elastic roll 32 (rubber roll) described in FIG. 4 and increasing the linear load.
  • the arrow LD indicates the length direction (take-up direction) of the stretched film and the arrow TD indicates the width direction of the film.
  • FIG. 4A is a process chart schematically showing an embossing process in one example of the present invention.
  • An embossing roll 33 of an embossing device 30 is composed of a steel roll 31 on which a predetermined zigzag or concave-convex pattern is engraved and the elastic roll 32.
  • the elastic roll 32 may be a compressed paper roll, compressed cotton roll or rubber roll with elasticity.
  • APTFE film is fed from a feeder 34. By passing between the steel roll 31 and the elastic roll 32 of the embossing roll 33, the PTFE film is provided with the pattern and is taken up by a take-up device 35.
  • the linear load of the embossing roll during the embossing process is preferably in the range of 0.1 to 1.5 kg/cm.
  • the temperature at which the embossing process is performed may be a room temperature (about 25°C).
  • FIG. 4B is a cross-sectional view and magnified cross-sectional view of the steel embossing roll 31.
  • the embossing roll has a zigzag surface, a pitch X between crests is set within the range of 0.1 to 1.5 mm, a difference in height Y is set within the range of 0.2 to 1 mm and a zigzag angle ⁇ is set within the range of 15 to 60°.
  • the embossed PTFE film By defibrillating the stretched PTFE film or embossed stretched PTFE film (hereinafter referred to as the embossed PTFE film) with the use of a rotating roll with implanted needles (pin-roll) or a pair of pin-rolls, a long PTFE multi-filament slit yarn having a network structure is obtained.
  • the pin-rolls whose needles have a diameter in the range of 0.3 to 0.8 mm and a length in the range of 0.5 to 5 mm are used.
  • the implanted needle density is in the range of 3 to 25 needles/cm 2 , preferably in the range of 3 to 15 needles/cm 2 and more preferably in the range of 4 to 10 needles/cm 2 .
  • FIG. 7 shows a preferred layout example of implanted needles in the pin-roll surface, the layout is not limited to this example.
  • the peripheral speed of rotation of the pin-roll is in the range of 50 to 500 m/min and preferably in the range of 60 to 300 m/min.
  • the film feeding rate is in the range of 10 to 100 m/min and preferably in the range of 20 to 60 m/min.
  • the PTFE real twist yarn of the present invention is obtained.
  • a single or a plurality of PTFE multi-filament slit yarns 51 are taken up by a bobbin 55 through a snail wire 52 and a traveler 53 on a ring 54.
  • Reference numeral 56 denotes a belt for transferring a rotation force and 57 denotes a spindle.
  • the traveler 53 is a C-shaped metallic part and is fitted in the flange of the ring 54.
  • the traveler 53 is pulled by the yarns and slides on the ring 54 at a rotation speed slightly lower than that of the bobbin 55, thereby twisting the PTFE multi-filament slit yarns 51.
  • FIG. 11 is an explanatory schematic side view of a ring yarn-twisting machine 60 when twisting a plurality of PTFE milti-filament slit yarns.
  • PTFE multi-filament slit yarns 62 taken out from a plurality of slit yarn bobbins 61a to 61d are converged by a guide wire 63 and are taken up by a bobbin 68 through a pair of nip rolls 64a, 64b, a snail wire 65 and a traveler 66 on a ring 67.
  • FIGS. 12A to 12D show twist directions in one example of the present invention.
  • FIG. 12A shows an example of a Z twist single yarn (composed of a single PTFE multi-filament slit yarn) and
  • FIG. 12B shows an example of an S twist single yarn. Either twist direction may be used.
  • FIGS. 12C to 12D show an example of a ply yarn (composed of a plurality of PTFE multi-filament slit yarns) and
  • FIG. 12C shows an example of lower S twist and upper S twist.
  • FIG. 12D is an example of lower S twist and upper Z twist.
  • the ply yarn is not limited to double thread and any number of yarns can be combined.
  • the PTFE real twist yarn of the present invention is preferably a single yarn composed of a single PTFE multi-filament slit yarn because it can be produced through a simple process and also the cost can be reduced.
  • the fineness D of the PTFE multi-filament slit yarn is in the range of 50 to 6000 dtex and preferably in the range of 400 to 3200 dtex.
  • the total fineness D of all of the PTFE multi-filament slit yarns contained in the PTFE, real twist yarn may be in the range of 50 to 6000 dtex and preferably in the range of 400 to 3200 dtex.
  • the twist of the PTFE real twist yarn is preferably fixed by heating.
  • the twist is fixed by sintering or semi-sintering the PTFE real twist yarn at 340 to 500°C and for 5 to 120 seconds, preferably at 350 to 470°C and for 8 to 60 seconds.
  • the twist preferably is fixed in the fixed length state or 10% or less stretched state.
  • the PTFE real twist yarn also has excellent strength and elongation properties.
  • the strength is in the range of 1.7 to 4.5 cN/dtex and preferably in the range of 2.0 to 4.2 cN/dtex.
  • the elongation is in the range of 3.5 to 40% and preferably in the range of 4.0 to 30%.
  • the PTFE real twist yarn of the present invention can be processed into application products that are required to have such properties as heat resistivity and chemical stability.
  • Examples of the application products include a sewing yarn for a filter.
  • the PTFE real twist yarn can be applied as a dental floss, which is required to have high lubricity.
  • the fineness D of each PTFE real twist yarn was measured on the basis of JIS L-1013.
  • the average fineness of filaments of each PTFE real twist yarn was measured in conformance with JIS L-1013. Specifically, the average fineness of filaments was determined as follows. First, in conformance with JIS L-1015 8.5.2, FIFE real twist yarn samples for microscopic observation were prepared. Then, the prepared PTFE real twist yarn samples were observed with a microscope (magnification: 100 ⁇ ). With regard to 50 filaments contained in each PTFE real twist yarn, microphotographs of cross-section of the respective filaments were obtained and then the microphotographs were processed using an image measurement computer software program ("APOLLO", model number: MML-3400, manufactured by Taiwan Textile Research Institute (TTRI)).
  • APOLLO image measurement computer software program
  • the number of twists T of each PTFE real twist yarn was measured in conformance with JIS L-1013 (A).
  • the ratio between the major axis width and the minor axis width of cross-section of each PTFE real twist yarn was determined as follows. Similarly to the measurement of the average fineness of PTFE real twist yarns described above, microphotographs of cross-section of PTFE real twist yarns were obtained and then the microphotographs were processed using an image measurement computer software program similar to the above mentioned. The longest diameter was defined as the major axis width and the shortest diameter was defined as the minor axis width.
  • each PTFE real twist yarn was measured in conformance with JIS L-1013 (A). Specifically, by using a constant-speed stretching tensile tester with an initial jaw separation of 30 cm, the tensile strength (cN) and the elongation (%) were measured at a tensile speed of 30 cm/min. A tensile strength and elongation at the peak of the obtained Stress-Strain curve were defined as the strength (cN/dtex) and elongation (%), respectively.
  • a circular bar with a diameter of 17 mm was obtained by mixing 80 parts by mass of a PTFE fine powder obtained from emulsion polymerization and 20 parts by mass of naphtha and subjecting the mixture to paste extrusion through a die with an angle of 60° at a RR of 80:1.
  • the extrudate was calendered between a pair of rolls with a diameter of 500 mm, followed by the removal of the naphtha at a temperature of 260°C.
  • the obtained original PTFE film had a length of about 250 m, a thickness of 0.2 mm and a width of about 125 mm.
  • a PTFE film having a thickness of 0.2 mm and a width of 25 mm was obtained by slitting the original PTFE film obtained in the process described above. Afterwards, the obtained PTFE film was stretched by 20 times in LD to obtain a stretched PTFE film having a thickness of 0.04 mm and a width of 5 mm. Thereafter, by using an embossing roll having an embossing pattern shown in FIG. 3A and a device of FIG. 4 ., a zigzag pattern was formed on the stretched PTFE film to obtain an embossed PTFE film. In the zigzag pattern, a pitch X between crests was 0.5 mm, a difference in height Y was 0.6 mm and a zigzag angle ⁇ was 45°.
  • the linear load of the embossing roll during the embossing process was 0.8 kg/cm.
  • the film was embossed continuously and entirely in the length and width directions.
  • FIG. 6 shows a PTFE multi-filament slit yarn production device in the present example.
  • the embossed PTFE film 12 was fed from a film feeding roll 11 and the embossed PTFE film 12 was defibrillated by a rotating roll 15 with implanted needles composed of a rotating roll 13 with needles (pins) 14 being implanted in its surface to obtain network structure fibers 16.
  • the fibers 16 were taken up by a take-up device 18 after passing through a guide 17.
  • the peripheral speed of the pin-roll was 200 m/min and the film feeding rate was 30 m/min.
  • the needle density was 6 needles/cm 2
  • the length of the needles was 5 mm
  • the diameter of the roll was 50 mm.
  • the distance between the needles A 0 and B 0 (axis direction) shown in FIG. 7 was set to 3 mm
  • the distance between A 0 and A 1 in a lateral direction (axis direction) was set to 0.5 mm
  • the distance between A 0 and A 1 in a vertical direction (circumference direction) was set to 3 mm.
  • a 0 to A 4 were oblique at regular intervals and the rows respectively beginning from A 4 and B 0 were also oblique at regular intervals.
  • FIG. 1 shows a network structure when spreading the PTFE multi-filament slit yarn in the width direction.
  • the size of each network cell was, when expressed by major axis ⁇ minor axis, in the range of 12 mm ⁇ 8 mm to 35 mm ⁇ 20 mm.
  • the arrow LD indicates the length direction of the film (take-up direction).
  • a real twist (Z twist, 450 T/m) was applied to the PTFE multi-filament slit yarn to obtain a PTFE real twist yarn.
  • FIG. 9 is a traced drawing of a cross-sectional image showing the cross-section of the PTFE real twist yarn of Example 1 obtained as described above.
  • the PTFE real twist yarn of Example 1 had a roughly circular (round) cross-section as the PTFE multi-filament slit yarn being twisted.
  • the cross-section had a circularity of 10/10, the number of the filaments 42 was 80, the fineness D was 1500 dtex and the twist coefficient K was 17428.
  • the PTFE real twist yarn had a strength of 3.0 cN/dtex and elongation of 6.67 %.
  • FIG. 2 shows a network structure when spreading the PTFE multi-filament slit yarn used in the production of the PTFE real twist yarn of Example 2 in the width direction. The ratio of the major axis to the minor axis of each network cell was roughly 1:1.
  • PTFE real twist yarns of Comparative Examples 1 to 3 were obtained in a manner similar to Example 1 except that they were Z twisted by the number of twists shown in Table 1.
  • Table 1 provides the production conditions, thickness and ratio between thickness and width of the PTFE multi-filament slit yarns used in Examples 1 to 4 and Comparative Examples 1 to 3, as well as the circularity, average fineness of filaments (dtex), number of twists T (T/m), fineness D (dtex), number of filaments, twist coefficient K, strength (cN/dtex) and elongation (%) of each of the PTFE real twist yarns of Examples 1 to 4 and Comparative Examples 1 to 3 measured as described above.
  • Table 2 also provides the results of sewing tests of Comparative Examples I to III using PTFE monofilament real twist yarns.
  • a PTFE monofilament real twist yarn having a circularity of 10/4, filament fineness of 1500 dtex, number of twists of 450 and twist coefficient K of 17428 was used. The twist was fixed by subjecting the yarn to a heat treatment at 450°C.
  • a PTFE monofilament real twist yarn having a circularity of 10/4, filament fineness of 1500 dtex, number of twists of 450 and twist coefficient K of 17428 was used. The twist was fixed by subjecting the yarn to a heat treatment at 425°C.
  • the PTFE real twist yarn of the present invention is also useful as a sewing yarn for web members, such as a highly thermal resistant felt, battery separator and bag filter, or prepregnation members.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (12)

  1. Fil torsadé réel (41) en polytétrafluoroéthylène (PTFE) obtenu en torsadant un fil de fente multi-filament (1) en PTFE, dans lequel le fil torsadé réel en PTFE a une section transversale circulaire avec une circularité dans une plage de 10/8 à 10/10, où la circularité est exprimée par un rapport entre une largeur d'axe majeur et une largeur d'axe mineur de la section transversale,
    une finesse moyenne de filaments est dans une plage de 1,5 à 200 dtx,
    une finesse D est dans une plage de 50 à 6000 dtx, et
    un coefficient de torsion K exprimé par la formule (1) est dans une plage de 10000 à 35000 : coefficient de torsion K = nombre de torsions T la finesse D du fil torsadé réel en PTFE 1 / 2
    Figure imgb0006
    où le nombre de torsions T représente le nombre de torsions par mètre et la finesse D est une finesse totale, caractérisé en ce que le nombre des filaments (42) est dans une plage de 10 à 200, et en ce que le fil torsadé réel en PTFE a une résistance à la traction dans une plage de 1,7 à 4,5 cN/dtx et une élongation dans une plage de 3,5 à 40%.
  2. Fil torsadé réel en PTFE selon la revendication 1, dans lequel le coefficient de torsion K est dans une plage de 11000 à 24000.
  3. Fil torsadé réel en PTFE selon la revendication 1 ou la revendication 2, dans lequel la circularité est dans une plage de 10/9 à 10/10.
  4. Méthode pour produire un fil torsadé réel en polytétrafluoroéthylène (PTFE), en particulier le fil selon l'une des revendications 1 à 3, la méthode comprenant :
    torsader un fil de fente multi-filament en PTFE en utilisant une machine de torsion de fil pour obtenir un fil torsadé réel en PTFE, dans lequel le fil torsadé réel en PTFE a une section transversale circulaire avec une circularité dans une plage de 10/8 à 10/10, où la circularité est exprimée par un rapport entre une largeur d'axe majeur et une largeur d'axe mineur de la section transversale,
    une finesse moyenne de filaments est dans une plage de 1,5 à 200 dtx,
    une finesse D est dans une plage de 50 à 6000 dtx, et
    un coefficient de torsion K exprimé par la formule (1) est dans une plage de 10000 à 35000 : coefficient de torsion K = nombre de torsions T la finesse D du fil torsadé réel en PTFE 1 / 2
    Figure imgb0007
    où le nombre de torsions T représente le nombre de torsions par mètre et la finesse D est une finesse totale, caractérisé en ce que le nombre de filaments est dans une plage de 10 à 200, et en ce que le fil torsadé réel en PTFE a une résistance à la traction dans une plage de 1,7 à 4,5 cN/dtx et une élongation dans une plage de 3,5 à 40%.
  5. Méthode pour produire un fil torsadé réel en PTFE selon la revendication 4, dans laquelle le fil de fente multi-filament en PTFE a une épaisseur dans une plage de 1,0 à 150 µm et un rapport entre une épaisseur et une largeur du fil de fente multi-filament en PTFE est dans une plage de 1/3 à 1/300.
  6. Méthode pour produire un fil torsadé réel en PTFE selon la revendication 4 ou la revendication 5, dans laquelle le fil de fente multi-filament en PTFE a une structure de réseau formée en défibrillant un film en PTFE en utilisant un rouleau rotatif avec des aiguilles implantées.
  7. Méthode pour produire un fil torsadé réel en PTFE selon la revendication 6, dans laquelle le film en PTFE est un film non étiré, un film étiré uniaxialement ou un film étiré biaxialement.
  8. Méthode pour produire un fil torsadé réel en PTFE selon la revendication 7, dans laquelle lorsque le film en PTFE est un film non étiré ou un film étiré étiré moins de 4 fois dans une direction longitudinale, le film en PTFE est étiré, après avoir été transformé en le fil de fente multi-filament en PTFE, de sorte qu'un rapport d'étirement total dans la direction longitudinale devient 4 fois ou plus.
  9. Méthode pour produire un fil torsadé réel en PTFE selon la revendication 7, dans laquelle lors de la production du film étiré uniaxialement, le film est étiré 4 fois ou plus dans une direction longitudinale.
  10. Méthode pour produire un fil torsadé réel en PTFE selon la revendication 7, dans laquelle lors de la production du film étiré biaxialement, le film est étiré 4 fois ou plus dans une direction longitudinale et 1,5 à 15 fois dans une direction de largeur.
  11. Méthode pour produire un fil torsadé réel en PTFE selon l'une quelconque des revendications 6 à 10, dans laquelle le film en PTFE est embossé linéairement le long d'une direction longitudinale et/ou dans une forme en zigzag ou concave-convexe dans une direction de largeur.
  12. Méthode pour produire un fil torsadé réel en PTFE selon l'une quelconque des revendications 4 à 11, comprenant en outre de fixer une torsion en chauffant à une température de 340 à 500°C pour une durée de 5 à 120 sec.
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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012105261A1 (de) * 2012-06-18 2013-12-19 Casar Drahtseilwerk Saar Gmbh Verfahren und Vorrichtung zur Herstellung eines Seils
JP5874626B2 (ja) * 2012-12-25 2016-03-02 カシオ計算機株式会社 表示制御装置、表示制御システム、表示制御方法及びプログラム
KR101307440B1 (ko) * 2013-01-28 2013-09-12 주식회사 텍스랜드앤넥스코 형태 안정성이 우수한 코드사의 제조 방법
KR101626892B1 (ko) * 2014-04-25 2016-06-03 주식회사서륭 인조혈관용 테프론 직물의 제조방법
CN105887221A (zh) * 2014-10-31 2016-08-24 陈路 一种用于制造ptfe缝纫线的多辊牵伸装置
CN106283309A (zh) * 2016-08-23 2017-01-04 上海伊贝纳纺织品有限公司 一种含有聚四氟乙烯纤维的混纺纱线及其制备方法
CN106868670B (zh) * 2017-04-12 2019-11-08 东华大学 一种聚四氟乙烯纤维/棉混纺纱线及其制备方法
CN106868669B (zh) * 2017-04-12 2019-10-08 东华大学 一种聚四氟乙烯纤维/毛粗纺纱线及其制备方法
CN113062000B (zh) * 2021-03-15 2022-07-22 上海灵氟隆膜技术有限公司 一种聚四氟乙烯牙线制备方法及系统
CN113046855B (zh) * 2021-03-23 2022-01-14 苏州大学 一种低线密度束状聚四氟乙烯长丝及其制备工艺和用途

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2772444A (en) 1954-08-12 1956-12-04 Du Pont Composition comprising a polyhalogenated ethylene polymer and viscose and process of shaping the same
SE392582B (sv) 1970-05-21 1977-04-04 Gore & Ass Forfarande vid framstellning av ett porost material, genom expandering och streckning av en tetrafluoretenpolymer framstelld i ett pastabildande strengsprutningsforfarande
GB1531720A (en) * 1974-12-13 1978-11-08 Tba Industrial Products Ltd Process for producing polytetrafluoroethylene products
US4168298A (en) 1975-09-22 1979-09-18 E. I. Du Pont De Nemours And Company Yarn consisting of drawn sintered PTF fibers and woven, non-woven and knitted fabrics; filter bags; ropes; and fire-protective clothing formed therefrom
US5281475A (en) 1991-10-17 1994-01-25 W. L. Gore & Associates, Inc. Continuous polytetrafluoroethylene fibers
KR100341078B1 (ko) * 1993-04-05 2002-11-29 다이킨 고교 가부시키가이샤 폴리테트라플루오로에틸렌섬유,그를함유하는면상물질및그의제조방법
DE69529746T2 (de) * 1994-06-30 2003-09-04 Daikin Industries, Ltd. Voluminöse langfaser und split-garn aus polytetrafluorethyten, verfahren zu ihreherstellung und herstellung von baumwollähnlichem material unter verwendung dieser faser und dieses garns und stoff für staubfilter
WO1996010662A1 (fr) * 1994-10-04 1996-04-11 Daikin Industries, Ltd. Fibre de polytetrafluoroethylene, article analogue au coton obtenu de cette fibre et son procede de production
US5718251A (en) 1996-04-26 1998-02-17 W. L. Gore & Associates, Inc. Dental floss article
JP2002194636A (ja) * 2000-12-20 2002-07-10 Daikin Ind Ltd ポリテトラフルオロエチレン撚糸ヤーン
BR0117150B1 (pt) 2001-10-16 2011-04-05 fibra torcida de politetrafluoroetileno expandido e processo de produção de uma fibra de politetrafluoroetileno expandido.
US6949287B2 (en) 2003-01-20 2005-09-27 Yeu Ming Tai Chemical Industrial Co., Ltd. Polytetrafluoroethylene fiber and method for manufacturing the same
JP4231797B2 (ja) 2003-01-20 2009-03-04 宇明泰化工股▲ふん▼有限公司 ポリテトラフルオロエチレン繊維の製造方法
US7131827B2 (en) * 2003-11-17 2006-11-07 Artemis Kautschuk-Und Kunststoff-Technik Gmbh Stator for an eccentric screw pump or an eccentric worm motor operating on the moineau principle
JP4471868B2 (ja) * 2004-03-09 2010-06-02 宇明泰化工股▲ふん▼有限公司 ポリテトラフルオロエチレン繊維及びその製造方法
CN100425746C (zh) * 2004-03-09 2008-10-15 宇明泰化工股份有限公司 聚四氟乙烯纤维及其制造方法
US7108912B2 (en) 2004-03-09 2006-09-19 Yeu Ming Tai Chemical Industrial Co., Ltd. Polytetrafluoroethylene fiber and method for manufacturing the same
JP4804061B2 (ja) * 2005-07-29 2011-10-26 日本ゴア株式会社 ポリテトラフルオロエチレン製のスリットヤーン
CN101074499B (zh) * 2006-05-18 2010-09-08 上海市凌桥环保设备厂有限公司 一种聚四氟乙烯长纤维的制造方法

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CN101929012A (zh) 2010-12-29
US8316629B2 (en) 2012-11-27
ES2385194T3 (es) 2012-07-19
JP5364461B2 (ja) 2013-12-11

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